Fully Atomistic Understanding of the Electronic and Optical Properties of a Prototypical Doped Charge-Transfer Interface

Gian Paolo Brivio, Anu Baby, Marco Gruenewald, Christian Zwick, Felix Otto, Roman Forker, Gerben van Straaten, Markus Franke, Benjamin Stadtmüller, Christian Kumpf, Guido Fratesi, Torsten Fritz, Egbert Zojer

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Abstract

The current study generates profound atomistic insights into doping-induced changes of the optical and electronic properties of the prototypical PTCDA/Ag(111) interface. For doping K atoms are used, as KxPTCDA/Ag(111) has the distinct advantage of forming well-defined stoichiometric phases. To arrive at a conclusive, unambiguous, and fully atomistic understanding of the interface properties, we combine state-of-the-art density-functional theory calculations with optical differential reflectance data, photoelectron spectra, and X-ray standing wave measurements. In combination with the full structural characterization of the KxPTCDA/Ag(111) interface by low-energy electron diffraction and scanning tunneling microscopy experiments (ACS Nano 2016, 10, 2365-2374), the present comprehensive study provides access to a fully characterized reference system for a well-defined metal-organic interface in the presence of dopant atoms, which can serve as an ideal benchmark for future research and applications. The combination of the employed complementary techniques allows us to understand the peculiarities of the optical spectra of K2PTCDA/Ag(111) and their counterintuitive similarity to those of neutral PTCDA layers. They also clearly describe the transition from a metallic character of the (pristine) adsorbed PTCDA layer on Ag(111) to a semiconducting state upon doping, which is the opposite of the effect (degenerate) doping usually has on semiconducting materials. All experimental and theoretical efforts also unanimously reveal a reduced electronic coupling between the adsorbate and the substrate, which goes hand in hand with an increasing adsorption distance of the PTCDA molecules caused by a bending of their carboxylic oxygens away from the substrate and toward the potassium atoms.

Original languageEnglish
JournalA C S Nano
Volume11
Issue number10
Pages (from-to)10495-10508
ISSN1936-0851
DOIs
Publication statusPublished - 24. Oct 2017

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Electronic properties
Charge transfer
Optical properties
charge transfer
Doping (additives)
optical properties
electronics
Atoms
atoms
reference systems
standing waves
Low energy electron diffraction
optical spectrum
scanning tunneling microscopy
Scanning tunneling microscopy
Substrates
Adsorbates
potassium
Photoelectrons
photoelectrons

Keywords

  • Journal Article

Cite this

Brivio, Gian Paolo ; Baby, Anu ; Gruenewald, Marco ; Zwick, Christian ; Otto, Felix ; Forker, Roman ; van Straaten, Gerben ; Franke, Markus ; Stadtmüller, Benjamin ; Kumpf, Christian ; Fratesi, Guido ; Fritz, Torsten ; Zojer, Egbert. / Fully Atomistic Understanding of the Electronic and Optical Properties of a Prototypical Doped Charge-Transfer Interface. In: A C S Nano. 2017 ; Vol. 11, No. 10. pp. 10495-10508.
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abstract = "The current study generates profound atomistic insights into doping-induced changes of the optical and electronic properties of the prototypical PTCDA/Ag(111) interface. For doping K atoms are used, as KxPTCDA/Ag(111) has the distinct advantage of forming well-defined stoichiometric phases. To arrive at a conclusive, unambiguous, and fully atomistic understanding of the interface properties, we combine state-of-the-art density-functional theory calculations with optical differential reflectance data, photoelectron spectra, and X-ray standing wave measurements. In combination with the full structural characterization of the KxPTCDA/Ag(111) interface by low-energy electron diffraction and scanning tunneling microscopy experiments (ACS Nano 2016, 10, 2365-2374), the present comprehensive study provides access to a fully characterized reference system for a well-defined metal-organic interface in the presence of dopant atoms, which can serve as an ideal benchmark for future research and applications. The combination of the employed complementary techniques allows us to understand the peculiarities of the optical spectra of K2PTCDA/Ag(111) and their counterintuitive similarity to those of neutral PTCDA layers. They also clearly describe the transition from a metallic character of the (pristine) adsorbed PTCDA layer on Ag(111) to a semiconducting state upon doping, which is the opposite of the effect (degenerate) doping usually has on semiconducting materials. All experimental and theoretical efforts also unanimously reveal a reduced electronic coupling between the adsorbate and the substrate, which goes hand in hand with an increasing adsorption distance of the PTCDA molecules caused by a bending of their carboxylic oxygens away from the substrate and toward the potassium atoms.",
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Brivio, GP, Baby, A, Gruenewald, M, Zwick, C, Otto, F, Forker, R, van Straaten, G, Franke, M, Stadtmüller, B, Kumpf, C, Fratesi, G, Fritz, T & Zojer, E 2017, 'Fully Atomistic Understanding of the Electronic and Optical Properties of a Prototypical Doped Charge-Transfer Interface', A C S Nano, vol. 11, no. 10, pp. 10495-10508. https://doi.org/10.1021/acsnano.7b05828

Fully Atomistic Understanding of the Electronic and Optical Properties of a Prototypical Doped Charge-Transfer Interface. / Brivio, Gian Paolo; Baby, Anu; Gruenewald, Marco; Zwick, Christian; Otto, Felix; Forker, Roman; van Straaten, Gerben; Franke, Markus; Stadtmüller, Benjamin; Kumpf, Christian; Fratesi, Guido; Fritz, Torsten; Zojer, Egbert.

In: A C S Nano, Vol. 11, No. 10, 24.10.2017, p. 10495-10508.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Fully Atomistic Understanding of the Electronic and Optical Properties of a Prototypical Doped Charge-Transfer Interface

AU - Brivio, Gian Paolo

AU - Baby, Anu

AU - Gruenewald, Marco

AU - Zwick, Christian

AU - Otto, Felix

AU - Forker, Roman

AU - van Straaten, Gerben

AU - Franke, Markus

AU - Stadtmüller, Benjamin

AU - Kumpf, Christian

AU - Fratesi, Guido

AU - Fritz, Torsten

AU - Zojer, Egbert

PY - 2017/10/24

Y1 - 2017/10/24

N2 - The current study generates profound atomistic insights into doping-induced changes of the optical and electronic properties of the prototypical PTCDA/Ag(111) interface. For doping K atoms are used, as KxPTCDA/Ag(111) has the distinct advantage of forming well-defined stoichiometric phases. To arrive at a conclusive, unambiguous, and fully atomistic understanding of the interface properties, we combine state-of-the-art density-functional theory calculations with optical differential reflectance data, photoelectron spectra, and X-ray standing wave measurements. In combination with the full structural characterization of the KxPTCDA/Ag(111) interface by low-energy electron diffraction and scanning tunneling microscopy experiments (ACS Nano 2016, 10, 2365-2374), the present comprehensive study provides access to a fully characterized reference system for a well-defined metal-organic interface in the presence of dopant atoms, which can serve as an ideal benchmark for future research and applications. The combination of the employed complementary techniques allows us to understand the peculiarities of the optical spectra of K2PTCDA/Ag(111) and their counterintuitive similarity to those of neutral PTCDA layers. They also clearly describe the transition from a metallic character of the (pristine) adsorbed PTCDA layer on Ag(111) to a semiconducting state upon doping, which is the opposite of the effect (degenerate) doping usually has on semiconducting materials. All experimental and theoretical efforts also unanimously reveal a reduced electronic coupling between the adsorbate and the substrate, which goes hand in hand with an increasing adsorption distance of the PTCDA molecules caused by a bending of their carboxylic oxygens away from the substrate and toward the potassium atoms.

AB - The current study generates profound atomistic insights into doping-induced changes of the optical and electronic properties of the prototypical PTCDA/Ag(111) interface. For doping K atoms are used, as KxPTCDA/Ag(111) has the distinct advantage of forming well-defined stoichiometric phases. To arrive at a conclusive, unambiguous, and fully atomistic understanding of the interface properties, we combine state-of-the-art density-functional theory calculations with optical differential reflectance data, photoelectron spectra, and X-ray standing wave measurements. In combination with the full structural characterization of the KxPTCDA/Ag(111) interface by low-energy electron diffraction and scanning tunneling microscopy experiments (ACS Nano 2016, 10, 2365-2374), the present comprehensive study provides access to a fully characterized reference system for a well-defined metal-organic interface in the presence of dopant atoms, which can serve as an ideal benchmark for future research and applications. The combination of the employed complementary techniques allows us to understand the peculiarities of the optical spectra of K2PTCDA/Ag(111) and their counterintuitive similarity to those of neutral PTCDA layers. They also clearly describe the transition from a metallic character of the (pristine) adsorbed PTCDA layer on Ag(111) to a semiconducting state upon doping, which is the opposite of the effect (degenerate) doping usually has on semiconducting materials. All experimental and theoretical efforts also unanimously reveal a reduced electronic coupling between the adsorbate and the substrate, which goes hand in hand with an increasing adsorption distance of the PTCDA molecules caused by a bending of their carboxylic oxygens away from the substrate and toward the potassium atoms.

KW - Journal Article

U2 - 10.1021/acsnano.7b05828

DO - 10.1021/acsnano.7b05828

M3 - Journal article

VL - 11

SP - 10495

EP - 10508

JO - A C S Nano

JF - A C S Nano

SN - 1936-0851

IS - 10

ER -